Fluorocarbons containing higher halogens have the potency of breaking certain hydrogen bonds in solutions. The relative strength of this potency varies in the series F < Cl < Br < I and the presence of hydrogen atoms in the fluorocarbon increases it. There is a striking parallelism between the hydrogen bond breaking and the anaesthetic potency of these molecules. It is suggested that the breaking of hydrogen bonds is an important step in the mechanism of anaesthesia. 相似文献
The reaction of alpha vinyl oxirane 5, prepared through a new route to the d-gulal system, with O-nucleophiles (alcohols and di-O-isopropylidene-alpha-d-monosaccharides) and C-nucleophiles (lithium alkyls) affords, in a completely stereoselective way, the corresponding 2-unsaturated alpha O- and C-glycosides having the same configuration as the starting epoxide. 相似文献
The enantioselective total synthesis of the actin-targeting metabolite (−)-microcarpalide is described. Key steps include ring-closing metathesis (RCM) for the final construction of the 10-membered lactone framework and stereoselective homologation of boronic esters for the insertion of all stereocentres with the desired absolute configuration. In particular, the acidic fragment was prepared in seven steps from a suitable chiral bromomethane boronate by means of two sequential stereoselective homologations to install the two stereocentres with the correct final R stereochemistry, employing (−)-pinanediol as the chiral director. Subsequent elaboration to the required C7 backbone entailed nucleophilic displacement with a vinyl Grignard reagent, oxidative cleavage of the boronic scaffold and protection-deprotection manipulations. Interestingly, when the tribenzyloxy diene ester resulting from DCC-mediated coupling of the two key synthons was subjected to RCM in the presence of Grubbs' catalyst, the reaction proceeded stereoselectively to yield the desired trans oxecin-2-one, albeit with poor conversion. 相似文献
A method is described whereby molecular symmetry is employed to reduce the number of two-electron integrals in perturbed Hartree–Fock calculations of second-order properties. The method is a generalization of the Dacre–Elder procedure. First- and second-rank perturbing tensor operators are examined in the coupled HF approach to electric dipole polarizabilities, magnetic susceptibilities, quadrupole polarizabilities, and spin-dopolar contributions to spin–spin coupling constants. The procedure sketched here permits a large saving of computer efforts, which is shown by some illustrative examples. 相似文献
Despite the large number of publications and patents concerning pH/thermoresponsive polymers, few data are available concerning the preparation of thermoresponsive cross-linked microspheres from preformed polymers. Therefore, N-isopropylacrylamide-co-acrylamide-co-(2-hydroxyethyl acrylate) copolymers were obtained as a new thermoresponsive material with a lower critical solution temperature (LCST) around 36 degrees C, in phosphate buffer at pH 7.4, and with a cross-linkable OH group in their structure. The LCST value was determined both by UV spectroscopy and microcalorimetric analysis. These copolymers were solubilised in acidified aqueous solution below their LCST, dispersed in mineral oil, and transformed into stable microspheres by cross-linking with glutaraldehyde. The thermoresponsive microspheres were characterised by optical and scanning electron microscopy, degree of swelling, and water retention. The pore dimensions of the microspheres and the retention volumes of some drugs and typical compounds were evaluated at different temperatures by liquid chromatography. Indomethacin, as a model drug, was included in the microspheres by the solvent evaporation method. Finally, the influence of temperature and of temperature cycling on drug release was investigated. 相似文献
Summary Un classico teorema di G. Gherardelli afferma che una curvaCP3 è intersezionè completa se e soltanto se è proiettivamente normale e sottocanonica. Qui si prova che, seC e a- sottocanonica ed inoltre le superficie di grado 1 + (a/2) (a pari) ovvero (a + l)/2 o (a + 3)/2 o (a + 5)/2 (a dispari) tagliano suC serie complete, alloraC è intersezione completa. Si determina inoltre un bound d funzione di a tale che, seC è a-sottocanonica e di grado d d, alloraC è intersezione completa se e soltanto se le superficie di grado a tagliano suC una serie completa. Si discutono poi numerosi esempi di curve sottocanoniche non intersezioni complete.Paper written while P. Valabrega was member of C.N.R. (G.N.A.S.G.A.) and both authors were supported by M.P.I. funds. 相似文献
An accurate gas-phase acidity for germane (enthalpy scale, equivalent to the proton affinity of GeH3?), ΔHacido(GeH4) = 1502.0 ± 5.1 kJ mol?1, is obtained by constructing a consistent acidity ladder between GeH4, and H2S by using Fourier transform-ion cyclotron resonance spectrometry, and 0 and 298.15 K values for the first bond dissociation energy of GeH4 are proposed: D0o(H3Ge-H) = 352 ± 9 kJ mol?1; Do(H3Ge-H) = 358 ± 9 kJ mol?1, respectively. These results are compared with experimental and theoretical data reported in the literature. Methylgermane was found to be a weaker acid than germane by approximately 35 kJ mol?1: ΔHacido = 1536.6 kJ mol?1. 相似文献
A new algorithm model-oriented for variable selection is presented in this study. It is based on the combination of genetic algorithms (GA) for hyperspace exploration, and counterpropagation artificial neural network (CP ANN) for deriving the fitness score. The proposed method performed very well on both well defined synthetic data sets and real academic data sets. 相似文献
In+As+Sb alloys have been deposited onto Ni and Ti cathodes from tartaric acid solutions at pH 2. Homogeneous deposits of composition suitable for achieving InAsxSb1−x can be obtained from this medium. The As-to-Sb ratio can be controlled by properly selecting solution composition and deposition potential.X-ray photoelectron spectroscopy and X-ray diffraction analyses show that formation of III–V compounds occurs at room temperature. In reacts preferentially with As rather than with Sb, but crystalline phases formed at room temperature are Sb-rich. After annealing the In+As+Sb alloys at 250°C, the composition calculated from cell parameters appears similar to that measured by energy-dispersive X-ray analysis, suggesting that the entire deposit has been converted into the InAsxSb1−x crystalline phase. 相似文献
Graphite electrodes were modified with triangular (AuNTrs) or spherical (AuNPs) nanoparticles and further modified with fructose dehydrogenase (FDH). The present study reports the effect of the shape of these nanoparticles (NPs) on the catalytic current of immobilized FDH pointing out the different contributions on the mass transfer–limited and kinetically limited currents. The influence of the shape of the NPs on the mass transfer–limited and the kinetically limited current has been proved by using two different methods: a rotating disk electrode (RDE) and an electrode mounted in a wall jet flow-through electrochemical cell attached to a flow system. The advantages of using the wall jet flow system compared with the RDE system for kinetic investigations are as follows: no need to account for substrate consumption, especially in the case of desorption of enzyme, and studies of product-inhibited enzymes. The comparison reveals that virtually identical results can be obtained using either of the two techniques. The heterogeneous electron transfer (ET) rate constants (kS) were found to be 3.8 ± 0.3 s−1 and 0.9 ± 0.1 s−1, for triangular and spherical NPs, respectively. The improvement observed for the electrode modified with AuNTrs suggests a more effective enzyme-NP interaction, which can allocate a higher number of enzyme molecules on the electrode surface.
The shape of gold nanoparticles has a crucial effect on the catalytic current related to the oxidation of D-(-)-fructose to 5-keto-D-(-)-fructose occurring at the FDH-modified electrode surface. In particular, AuNTrs have a higher effect compared with the spherical one.